lR/,\ MoRAhla` ANDR1E] cotĄLAl Influence of comPatibiliz€r łTe

lR/,\ MoRAhla` ANDR1E] cotĄLAl Influence of comPatibiliz€r łTe

52
I MlPo-LĄ\
]lR/,\ MoRAhla'II,ANDR1E] cotĄLAl
ANDRZE GAJ.ESK
EWA IIOPKOWSKAIT
5loLl'''
Influence of comPatibiliz€r łTe' PolyPloPylene moleculat weigth and
blending sequence on ńontmo llonite exfoliation in nano.omPosites
RAPID COMMUNICATION
sunmary Mortmorilloniteeiloliationi"polynermaruisacrucDlhdor
obiłi|inE a ńat*i.llrirh jmPoved baiiiet PloPshcs, r€dured fbnmibi.
lit' hj8herela*t ńod!l$ and bńsilc *leryrh. onc of the włys lo obtajn
PolyPoPyl.ne bafd nanmońPolie włh ńońfuorillonile ilvolles an aPpli
.atjonof otpihbiljzss,forcx' Plcmalcicanhydridootaayli.aĆid graftd
Pol],PrcPyl.m Thc cliccts of blcnding scqucnre' polyprÓPylene ńolEula!
w.ighi' ald Propeti.s ol ł ĆomFatibil'd otr .x fuliation of monhoi llo ni tc
I{tr
prcpylcnc, monrmorilon e, exroliatiotr,
Polyńc! ba5cd nańo<,ńFolics Wirh ńonfuolillo
nite IMMT) arc
rŃńdy
th!
\Ubjd
.(d silic.t. con'
sjślńg ofrnń th(k l'ycr' lńth ga]lffm bdwccn thcn
omPicd by ark.li shons rn thcp
nE,brc vith hyd roph i li. polynrB. ExdmnSe or ihosc
.łiions with .aiioni'orEali. sur
ot c M]VrT.ompaiibilitylfi thothcrl!ŚhydrcPhiliĆÓl
elen hydlophobi. Folymeś.
DispeBionand cxnnia onoIMMTiń i Polymsma
tiiallo\4 lonodify ihc PfuPctics of th.ńatcń] _ to
.Dh. n ( thc bificr ol Sascs . nd vapous pcrne ion, b
rcducc flammibiliry and to implore iheinal sabilir),
fic prcsncc or exlolia&d n,ortmo
żn n(rcasc ol ihc modulLE Il lensil! śt.lgth'lm
provcncnt ol pbpsrics is usuilly ob
d Ą' loi d inE, noi ex.ed ing scvcra l Nlighi Pol .Ćnh '
NanocomPosit.s witl' ]Vl]v'T bł
PolyProPrlerc (iPP) lve! alj) obraińcd nr thc p'śłnd
| ,nPo in.. of this
polyńdlrl Rcfclcn.cl2l(rcwsthcbułcsleadingb
M MT na nocompGi t.s bi sd on iso tadic polyPrÓPylcnĆ
ThcPcsibiliq,ioobtaine Óliłbd MMTbvńcltńi{mg
ol oĘano. modiIiod lVllVlT \'iih PolyFroP]'Lcn._ Eraficd
nalcic nryd ]e jsal$fuPofud l3l Thcuscofmłlci.
a' lydride ńodificd FroPvLc|c oLi8oncFas comp.li
bil'et
fo. IPPIMMT
syseń was ako skĆ*s'ully .x
ofsaleies, whjrc MMTcr
foliiijon iNÓlves a cońPl.lc scP' E hon ol.li]' li]'os
Boih elf..ś6n bcsfodicd ciihcr by high rcsolution mi
dosÓpy likc clc.hon hłnsmission mi.m{oPv or bv
x tay sidc an€lc difrłdiondne io a rś!ędiv.ly sńall
intelliyodishn.* o1MNfI Pa iĆlc! l5]'
tn thc Pres€ni papł we inve*isal. the Ćffi.icncy of
dllferenr .omparibirizcG, ihc innucn.c of mohculir
weight of PÓlyProPvlcne and lhe bleMin8 mntlitions otr
exIo1iatn,n oI oĘano-modified m
Foly PlÓPy h nc bł*d MnoÓmPÓsit! sv*enl '
ch.rns r6uus inbroadenins
Fo r ncar polypropylcncs an,r tlrc. grancd pol),pn)
Fylens lscd łs .ontl]libiliŹos, lis
rsld b plcparc ur composit* Th
woght.nd henĆ.]nńdt oory ntc (M|{)
ihcm
ihc polish PrÓdud Włh broidcr molcculir wcighi
^moĘdistiPolypropylcne .ompatibilize^ ws.i adyln r(id
3lafbd PolyProPy]ene (6 lł' ,1' (,f flndi,nal souPs)
and ńalcic anhydtidg gtalbd Fol)'PloPyLcn. o r( ,]
and 0 5 wt '/o ol Iun.tional !tr!Pł rli8her ońccnta
tion of mil€ic
glouPs lcads Unavoidłbly in
'Lndioml to h,!hc! MrF
thc cisc ol polypnpylenc
POLIMERY 2004,
Tabl
49, nr 1
e 1' characteristi.Ś
53
of polymeric comPońants used in nano.ońpÓsites
oC)
3 0 (230
Ma]cn PF401, orl€n, Polan.{
Novolcn l1ootl. BAs!', Gcrńanv
PIH
r 8 (230
Novol.n ] l0(]L, l]A5Ę C]crmany
Novol.n ]l00N, BAsĘ ccma|y
5
'C)
'10 090"c)
]l009r "c)
col I30Ę shovring Pcrlodicity of2'2 nm.
composites coniairling 1PĘ a conpatibli1izer and
MMT were obtained by two,step blcnding in a Brabendcl intenal mixer during 20 mrn mixing ar 60 rpm. Two
\ĄIays ofsamPle PreParatiol wele used:
A. iPP and a comparibilizer were blended
- toRoute
prior
addition of MMT, boih blendnr8 sieps werc colrducted at 170 oC.
B. A compatibilizer was first blended wirh
- inRoute
MMT
weight proportion of 10:3 and later added to l?p
melt. The firct blending siep was conducied at 200 oC
(B1) or at 170 oC (ll2), while the second blendinS step
was carried out always at 200 oC.
Compos jtion of compatibilized sysiems and btending
icmperaturcs are listed Table 2. For comparison, the
sa'nPle .ÓdeŚ, .omPositionŚ and blćńdi.g temPerntu.e
B loltes ol ŚamPl€s Pr.pa.ations' M de'
duinabothstePs oi A and
montrnor
5
5
105
ac.ylicłcid,6 wt''l,
malcic anlr-\'dridc' ] trł. 'r'
malciĆ anhydridc, t].5 wt l
composites of iPP with MMT bur .ithout a compatibilizer were also obtained in one-pot btending proce,
durc: both Ćo ponents were dry-biended and then ńelt
intcmal mixer at 200 oC.
0.5-0.8 mm thick films were obtained from chunks
of blended materials by compression motdhg at 200 .'C
for 3 min follorved by cooling in warer.
mixed
Pleparation oI samples
nÓt€s
2.5
5t 090"c)
MMT used was a Ćommelcial Ploduct of Nanocoł
USA, octadccylamine modifiec:l montmorillonite Nano-
Table 2'
3t.los
(ł0oc)
111230't)
Polybond 1001, L.rni.oval
Polvbond 3200, Lrni.oyal
Polybon.l 3150, Uniro)ral
preparation
jlloni1.
il1 a Brabender
Methods
The composites were ciaracterized by wide angte
X-ray diftuaction (WAXS) ln ihe h.ansmission mode and
by transmission elecŁron micloscopy oEM). WAXS sys
tem consisted of a computel controllcd wid€ anglc goniomcter coupled to a sealed tubc source of CuKaradia
tion, operating at 30 kV and 30 mA. The CuKo tine was
filtered using eicch.onic fiitedng and the usuat thin Ni
filtcr. The slit system that was used for cottecting 2()
scans allowed for the cotlection of thc diffracted beam
with a divergence angle ofless ihan 0.05 deg. MMT parl .I{'5 Jlone Were dl"o studled b) rĄ ĄXs r,'l .onP lr]"^n
Ulhathin sections of ihe films were cryo ulLramicro
tomed and studied by means of transmission electron
microsĆoPe (TEM) Tesla'
RESULTS AND DISCUSSION
Dt:2(rOl200 "C
Bl:200/2(l(r'C
tJl:200/200 "C
Dl:2(r0
/200'C
Ll1:200/200'C
Bl:200/2(r() ''C
57133llr
B1:200/201r oC
200't
200 "c
200"c
9(r,10
tll:201r/200
"C
lJ2: 1701200
oC
A I70lr70
0C
tsl:200/200 "C
t|H/
PDI
B2: 17o /21)O
/M6^
|'Pl /Pbl/Nlb]Ż
]'Pl /llJ /Ńlb.
71:21)
6
7+2l 'ó
B1
:
200 / 200
ts2: 17A / 2AA
^:170/
"C
0c
"C
l7A"C
TEM examinaiion (Fig. 1) showed a targe amount of
exfoliaied monimo llonite in all ĆomPatibilizc.t sys
trms, although nanoclay parricles wiih preserved mulrildyercd .truLturF wcre.,1-o nb.crved. Clo>rr cx.rmrna.
tion of the micrographs shows rhat the exfotiaiion process starts from the ed8es of montmorillonite parricles
']'ld proCc€o5loń 'lrdc lhc l celltrr.' Such le',tllr' oferlo
liation sirongly suggests the importancc of duration and
intensity ofmixing and also of inreracrjon htcnsity with
r€active comPatibilizers'
X-ray diffraciograms of MMT and selected nanocom
posites are demonstrated in Fig. 2 and 3. X-ray diffracio,
gram of MMT shows a charaĆtelistic peak ai 20 = 3'9
deg, which corrcspolds to spacing of2.2 nm. Thc peaks
remained well visible for PPF/MMT composiiions without comPatibi1iŻer' In X_ray diffraĆtoglams of ĆomPati
biliŻed systems usually the declease in ihe peak hcight
and il_ -hlri toward5 _m'lllcr \ł ue\ ol 2o lr8ll '\;r.'
POLIMERY 2004,49, nr
54
1
I
rl
13it9
2O,de8
FĘ' 2' X-ruy dit't'ractoyans of MMT and
Cnmpatibil1zcd
polyprapylcne based na ocomposites uith 3 wt.'1, of
(prepnratian
3
as
MMT
B1)::1- MMT,2
- PPFIPBAIM3N,
PPF|PB||M3H,4 PPFlPB2lM3u.
Codes ofsanpLes
-h Ttbb
rcLtte
2
1
L
;6
5
lt
,
EiS. 1. TEM mirognphs ol canpatibilizcd pallpropVlene
bąsed nanocampositcs u,ith MMT: a) PPH|PB1|M6 , b)
PPHlPBllM6,\, c) 1'l'NlP81lM6A, Ll) PPLlPBllM6A. Codes
of samples as
in Tablc 2
observed duc io cxfoliaiion and broadcning of ihc inter-
platelet distancc rcsultin8 Irom intcrcalation by compatibilizer an.1 polypropylene chairrs. As it is seen from
Fi8' 2 and 3 these effects depend, howeveł on the nanocompositc preparation routc and on composition.
ll51I
2 O. deg
Fir' 3. X-fi! diflractagafis af comPitibi]Łed po|yłapllene
base1l afiocomPasites 70ith 6 wt ' % af MMT łepared usilLs
ło tes A and B aru1 PB1 conpatibi|izer: 1 PPNIPB1lM6A,
PPLIPBIIM,A,3
PPHIPBIIM'A,
4 '
ppLlpBllM6Br,6
ppHlp81lM682,
PPNIPB:LlM6B2,5
7 PPNlPBl.lM6d,8 - PPL|PB||M,N, I
2
PPHlPBllMq
.
Ca!1es of samples
as'in Ttble 2
lcrdiĘ b nNt.IliĆi.|t eYn]lńhon whil. PBA was the
woEt anong tn. ońFatibilia6 uscd in this l'olk' as it
As itis sccn in Fis. 3 rhc isoh.ri. porypropylcncmolc.ulal weight has no siBnilidnt inaucn.c on ńc exlÓ
liaiiolaId inteńlatjon ol M,v'T when the ÓmPolitcs
were obbin.d by brcndin! In* polypnpylene \inh a
ĆońPatibiljzcr at 170
and then with MMT Goutc
t
APP'rcndy thediluiionof PÓlyPn,Pyle|swith ]owvis.
^)
cous comP ibilizeB signifiĆantly lcducs thc diff.F
cnccs bcnvecn rhc porypbpykns by lowc ng their
Roub E2, by PĘPalatn]n oI a ms
patibili€rand MMTal r70 !c and th en
polypnPylene ł 200 oc aPP.aE l
bl. ndin8 with
Al5o h c ih c no]Ru]ar weĘh t !l PolvPlopy Lcnc
Flays littlc rclc in exrolbiion and inrcrcabtion or MMT.
This obscrvaiio| i'ldi.ates thł thc
lEiion ]d iŃd.alatioń bkes P]i.c du n8 plepłatiÓn
oI ł ra*Ćlbakh of MMT tvith .ompalibiliŻei sub
selu.nr blcndins of rhc misrcrb .h wirh polvpn)pylc
n* iśnot mu.h clfcdivc in lLrdrer
calaijon of MMT This k ihe l.asÓn of kN lnf|ucmc oI
thc molc 1ł woiBhl Óf pÓlyPloPylcn* on ihc cxfolia_
rig 3
exfoliation
_
larB.r
Itcd in l$s rfii.ient
ładion of non.cxfoliated day Pańi
The reslhs obt ined tudi.are that the sequcn.c oI
blending plays a oucial role in
ńonhorillonłe efolii.
tjon in rhese thr@ .omponlnt syś.ńs _ PolyProPylenc'
ńontnońllonih and a ońPahb izcr ThP best HulE
\'ele obtained by FrePłahon of .ompatibil'er/MvT
ń6lmLł1th Iolloved by meli blendilg with a ńr Polypropylcne. A.ryhc a.id grafred polypropylene was
found signifiĆandy lcs .ftedi\'. than naleh anhydDdc
gmf rPd poryPloPylcncs.
obtained \'ben
usiĘ
Howelri
a .omPatibili2er Wilh smaucr
.on-
ńalci. annydride graIied but shoving highel vk
.osity Thk observłńn Poinb out thłt not only lhe
inou|t of rłĆtive ErouPs is inpor
.o!ty durinB nirins, which influe
olshlii Fot hishm vis.ciry l€ shear k baa!ńiit.d to
p iicr* mor. cfficicnity T]p innlencc ot the bmpcnruN or the masrerbakh pFpararion also indic ?s rhc
Positive effcd oI hiBher li(osjry duliĘ blcndiĘ PrG
.!$ o n MMT exlÓliańoń ll thc miśeńa th is prepatd
at hlghcr lenPdżfure'
.i lowPr vkcosiiy ofa ĆÓń
Ient Óf
Pahbi]izcł then rhe
noholir
'.
weight 01PolvPloPylenc
ma*łbaEh uscd as a marix should be as high as po$ibt. ro cnhancc
prePanlion tÓ 200 !c lcd to s]mihllv elli.icŃ !'IÓliatiE
in rh!Ćasc of hi!hcrnolc.ulal weĘht.IpDlyPoPyhnc
ded to PPH ryPc of
porypropylcnc (rcurc B) Howeve!, nr thc case of ppN
Thś u,k t?Ś ptlklly nlppaĄ.1 by !
i|d PPL polyprÓPvlĆncs, thc .lfoh ion was les .fii It sl[llifn fuirrh (Polrhl),Tth|]inl t/łi!łśifu,I L."1:
o. than in the .łse l'hen rhc ńż*clb .h was Pre rń c. Ę af l\kLa ł i Mr.nh
Prredai170oc' haPPeaĄ lhathigh ntl.mlalwei8htof
polyprcpvlenc enhancs tosome extlni tlr po,cb ion
of polyn!łi. .onPon.nt into 3ł11
RIIIERENCIS
tion .f MN'IT p]iicleb duriĘ drc n.It blcndnrs oI lhc
ńaśsbakh ind Polypropylene
Thc r€n'lh obtaiftd nł PPLind PPFarcesotially
$!ril'rb.ouse they sholvsjń a!M.ł
PolyProPylen.molc.llarwcight ftcbd aLo the FÓ
3 H6egłw; N, okJDroIo H, (ar
sition of p.ak lelatd to MMT inkrplalelĆt diśżn.c,
whi.h is beśvisiblc fol nano.onPNilos PĘPar.d ic.
.odi'Ę b rhc roub Bl,200.c/200.c'Thc Pcik shift
towards Śmallcl 20 Yaluc incrose
s.i m , s3.
poltproptlenc moleular wcight indi.atin8 ihc broadf the
łł
a'iĘ
of rhc
effi.icnt
dist
.c betrcon day F
Ńerablion
by PolyproPylcnc
llraiN' Usually,